Process for developing silver halide color photographic light-sensitive materials at high temperature

ABSTRACT

A DEVELOPIONG PROCESS WHICH COMPRISES SUBJECTING A MULTI-LAYER SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL TO HIGH TEMPERATURE PROCESSINGS IN THE PESENCE OF A COMPOUND REPRESENTED BY THE FOLLOWING GENERAL FORMULA   2-R2,5-R1,6-R3,7-HS-S-TRIAZOLO(1,5-A)PYRIMIDINE   WHEREIN R1 AND R2 WHICH MAY BE THE SAME OR DIFFERENT, EACH REPRESENTS A HYDROGEN ATOM, AN ALKYL GROUP, AN ARALKYL GROUP, AN ARYL GROUP, OR A HALOARYL GROUP, AND R3 REPRESENTS HYDROGEEN ATOM, A HALOGEN ATOM, OR A ALKYL GROUP IS DISCLOSEC.

United States Patent Oflice 3,741 ,765' Patented June 26, 1973 Kanagawa, Japan No Drawing. Filed Dec. 16, 1970, Ser. No. 98,880 Claims priority, application Japan, Dec. 16, 1969, 44/101,117 Int. Cl. G03c /30 US. Cl. 96-66.3 14 Claims ABSTRACT OF THE DISCLOSURE A developing process which comprises subjecting a multi-layer silver halide color photographic material to high temperature processings in the presence of a compound represented by the following general formula I SH wherein R and R which may be the same or different, each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a haloaryl group, and R represents hydrogen atom, a halogen atom, or an alkyl group is disclosed.

BACKGROUND OF THE INVENTION (1) Field of the invention The present invention relates to a process for developing color photographic materials. More particularly, the present invention relates to a rapid developing process for color photographic material at high temperatures.

(2) Description of the prior art A multiple layer color photographic material has at least three superposed silver halide emulsion layers having different spectral sensitivities on a support. For instance, in the case of a typical color photographic material, a red-sensitive emulsion layer, a green-sensitive emulsion layer, a yellow filter layer, and a blue-sensitive emulsion layer are coated on a support in this order.

One aspect of the progress in recent photographic processing engineering is the speeding up of processing by raising the temperature of development (higher than 30 C.). This is usually called high temperature rapid processing. One of the disadvantages occurring in the high temperature rapid processing of multi-layer color materials is that the uppermost layer is developed excessively before the bottom layers are completely developed.

It is known that to overcome this drawback a development inhibitor is added to the developing solution. However, when the development inhibitor which has usually been used, such as a fi-nitro-iso-indazole compound, is added to a developing solution, not only is the development of the uppermost layerv inhibited but that of the bottom emulsion layers also is inhibited.

In order to avoid this disadvantage, the addition of an acyl-amino-phenyl mercaptotetrazole compound to a developing solution or a photographic emulsion layer is known to be effective, because the development of the uppermost layer is selectively inhibited by the compound and the balance of the entire development is improved (see US. Pat. No. 3,295,976). However, the mercaptotetrazole compound described in this patent has the difficulty in its synthesis since the raw material for the compound is thiophosgene which is generally difiicultly available.

An object of this invention is to provide a high temperaturerapid development process for multiple layer silver halide color photographic materials using an effective development inhibitor for the uppermost layer.

SUMMARY OF THE INVENTION As the result of investigations of various compounds we have discovered that the desired effect can be obtained by adding to the developing solution a mercaptotetraazaindene compound which can be readily synthesized. Y

According to the present invention, by adding a mer- DETAILED DESCRIPTION OF THE INVENTION As a processing solution prior to the development, there is usually employed a pre-hardening bath, that is, an aqueous solution containing an aldehyde for hardening the gelatin in a photographic emulsion layer, such as formaldehyde, glyoxal, succinaldehyde, glutaraldehyde, andthe like. The aqueous solution further contains a salt such as sodium sulfate, a pH-controlling agent or a buffer agent, such as borax,,boric acid, acetic acid, sodium acetate, sodium hydroxide, sulfuric acid, and the like, and also an antifoggant for development, such as an alkali metal halide. The development inhibitor of this invention can be added to such an aqueous pre-hardening solution.

When a neutralizing bath is employed for preventing the aldehyde in the pre-hardeliing bath from being carried in the developing solution, the development inhibitor of this invention can be added to the neutralizing bath. The neutralizing bath contains an aldehyde-scavenging agent, such as hydroxylamine and L-ascorbic acid,

, and it can further contain a salt and a pH-controlling agent or a butler agent.

The black & white developing solution for reversal color photographic films contain at least one of the developing agents such as hydroquinone, 1-phenyl-3- pyrazolidone and N-methyl-p-aminophenol. The developing solution further contains a salt such as soduim sulfate, a pH-controlling agent or a buffer agent such as borax, boric acid, sodium hydroxide, sodium carbonate, and the like, and an alkalimetal halide. The development inhibitor of this invention can also be added to the black and white developing solution.

As a color developing solution for color negative films and color papers, there is usually used as alkaline aqueous derivative as a color developing agent, such as N,N-diethyl-p-phenylene-diamine sulfite, N,N-diethyl-3-methyl-p-phenylenediamine hydrochloride, 4-amino-3-methyl-N-ethyl-N-methanesulfoamidoethyl aniline sulfate, 4-amino-3-methyl-N-ethyl-N-hydroxyethyl aniline sulfate, N-ethyl-N-hydroxyethyl-p-phenylene-diamine sulfate,

and the like. The solution further contains a salt such as sodium sulfate, a pI-I-controlling agent or a bufler solution containing a p-phenylenediamine agent such as sodium hydroxide, sodium carbonate, sodium phosphate, and the like, and a conventional antifoggant such as an alkali metal halide. The developing inhibitor of this invention can be added to the color de velopment solution.

The objects of this invention are attained by adding a mercaptotetraazaindene compound represented by the following general formula wherein R and R which may be the same or different, each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a haloaryl group and R represents a hydrogen atom, a halogen atom or an alkyl group, to any of the above-described processing solutions.

Typical examples of the compounds to be used in the invention represented by the above general formula are shown below although the scope of this invention is not to be interpreted as being limited to these compounds. I

Compound 1: 1,3,3a,7-tetraazaindene-4-thiol C I \CH I SH Compound 2: 6-methyl-1,3,3a,7-tetraazaindene-4-thiol n e-Z \O H N Compound 3: G-tertiary-butyI- I,3,3a,7-tetraazaindene-4- thiol Compound 6: 6-undecyll,3,3a,7-tetraazaindene-4-thiol n-CnHn|C' 3 \O Compound 7: 6-heptadecyl-l,3,3a,7-tetraazaindenc-4-thio1 Compound 8: 6-phenyl-l,3,3a,7-tetraaZaindene-4-thiol I HC N I SH Compound 9: 5-bromo-6-methyl-l,3,3a,7-tetraazaindene- 4-thiol Compound 10: 2,6-dimethyl l,3,3a,7-tetraazaindene-4- thiol SH Compound 11: S-ethyI-IS-methyl-1,3,3a,7-tetraazaindene- 4-thiol H C N Compound '12: 5-iso-butyl-6-methyl-1,3,3a,7-tetraazaindene-4-thiol I isoH 0 -c N 7 s (I) N SH The compound represented by the above-described general formula can generally be prepared by reaction of aminotriazole with an acylacetic acid ester, the product then being reacted with phosphorus oxychloride, and after extraction, the extract being reacted with thiourea.

SYNTHESIS EXAMPLE (Compound 3) Aminotriazole and an equimolar amount of 4,4-'

Other compounds can also be synthesized by the process First and second stopping solution: described in the specification of British Pat. No. 893,428. Acid acid cc 25 It is disclosed in the specification of British Pat. No. Sodium acetate g.. 25 893,428, that by adding the compound represented by the Water added to make 1 liter. general formula above to a silver halide, the storage- Color developing solution, stability of the silver-halide on storage was improved and Sodium hexametwphsphate g 1 the thermal stability of the silver image obtained was in- Benzyl alcohol "3 6 creased. However, the use of the compound in this in- Sodium sulfite vention is fundamentally different from the disclosure of Sodium phosphgt'e the British patent. That is to say, in the case of subjecting 10 Potassium bromide a color photographic light-sensitive material to high tem- Potassium iodide perature processings, such phenomena frequently occur Solution cc 100 that the uppermost layer thereof is excessively developed sodium 6 and a change of color balance occurs. In this case, with 4 amino 3 ;]-:-I:I:-e-fi;i ;;&1 m; high temperature development in the presence of the comsulfonamidoethyl aniline sulfate g 10 0 pound of the present invention, an image having improved Ethylenediamine 2; color balance can be obtained without being accompanied Water added to ;i'{ by such disadvantages. Thus, it can be said that the high temperature processing for color photographic light sensi- Bleaching solution: tive materials cannot be practiced effectively without em- F rrlcyan nde g 100 ploying the process of this invention. Each of the com- P ta lum br mide g 30.0 pounds represented by the general formula set forth above Water added to make 1 liter. can prevent the excessive development of the surface layer Fixing Solution. or the uppermost emulsion layer and development proc- Sodium thiosulfate 150 essing glvmg good color balance can be conducted. Sodium sulfite 10 gmpangttheseucompounds, however, compound 3 can give Wat?r added to make 1 men e es resu s.

The amount of the compound of this invention to be In the abVe'deSeT1bed e l development Ph employed can be varied according to the type of the comesslhgs, the eofhpouhd Of t IIIVBIIUOII a ed to the pound, the type of color photographic material to be used, black and Whlte developing f p h, and the nature of the composition of the processing soluthe e P h Was l e llslng a black and Whltfi tion. In general, however, the amount of compound used developlhg h h fohtalhlhg conventionally kIlOWIl can range f 1 to 1 g. liter f the processing antrfoggant, 6-n1tr1o-1so1ndazolelinstead of the compounds solution of this inventlon.

The optimum amount of the compound depends upon many factors, such as the compound to be employed, the Test No gg ggggg g gggg Amount additive composition of the processing solution, the activity of the developing solution, the processing temperature, and the 2 compoun d1 zoxwsmolemer properties of the multiple layer color photographic light- 3:" I Compound 3:" Do. sensitive material. 40 gfi'nitigisoindawle 5 365 mole/liter The invention will be explained below in greater detail by reference to the followmg examp The results obtained are shown in the following table, in

EXAMPLE 1 which the blue density (D and red density (D A multi-layer color reversal film composed of three of the e? P? of the test Strips (maximum deneity silver halide emulsion layers contain difierent couplers Part) Sensltlvltles for Ted and blue exposures are 11st and having dilferent spectral sensitivities was exposed ed to ate the photographic effect. using a sensitometer and then subjected to the following procedures Maximum density Sensitivity 1 Blue Red Test No density density Blue Red Te p 2.4 3.4 175 115 ature, 3.4 3.5 100 100 Process C. Time 3'5 99 98 Black and white development 37 3 min 98 2; First stopping 37 30sec teeterin i3 team 30 .nt rr tti t tr 553 relatively by Second stopp ing 37 30 see I w y 0 es 0' eng giilc hhfiffff j; n 30 SW AS Shown in the above table, the addition of the comi i g u" fi u i pound of this invention, a good image quality having a The compositions of the processing solutions used in the above processings were as set forth below:

Black & white developing solutions:

Sodium hexa-metaphosphate g 1.0 l phenyl 3 pyrazolidone g 0.3 Sodium sulfite g 50.0 Hydroquinone g 6.0 Sodium carbonate (monohydrate) g 35.0 Potassium bromide g 2.0 Potassium thiocyanate g 1.0

Potassium iodide (0.1% aqueous solution cc 10.0 Water added to make 1 liter.

sufiiciently high blue density and a good balance of blue density and red density was obtained without reducing the sensitivity. 0n the other hand, in the experiment of using 6-nitroisoindazole instead of the compound of this invention, it was confirmed that if the amount of it was small, the effect of increasing the blue density was small and if the amount is large, the sensitivity was greatly reduced although the blue density increased, thereby good image quality was not obtained. In other words, with the known developing inhibitor, the development of both the uppermost layer and the bottom layers were inhibited. On the other hand, using the compound of this invention, the excessive development of the uppermost layer by the high temperature development was prevented, the development was conducted with a good balance, and no reduction in sensitivity occurred as shown in the above-described table.

7 EXAMPLE 2 A multiple layer color photographic film prepared by coating a cellulosive triacetate film with a red-sensitive 'gelatino silver iodobromide emulsion layer, a green-sensitive gelatino silver iodobromide emulsion layer, a colloidal silver-containing gelatino yellow filter having blue absorption, and a blue-sensitive gelatino silver iodobromide emulsion layer successively was exposed using a sensitometer and then subjected to the following processmg.

Tempera- Process ture, C. Time Pre-hardening 40 30 sec. Water washing 40 Do. First black and white developmen 40 76 sec. Water washing 40 30 sec. Reversal exposure (red light) from the back face of the film 200 cms. Cyan color development 40 180 sec Water washing 40 30 sec. Rev ersal exposure (blue light) from the front face of the film- 200 cms. Yellow color development 40 90 sec. Water washin 40 30 sec. Second black and white development 40 15 sec. Magenta color development 40 120 sec. Water washin 40 60 sec. Bleaching 40 Do. Fixing 40 Do. Water washing 40 Do.

The compositions of the processing solutions used above were as set forth below.

Hardening solution:

Sodium hexa-metaphosphate g 1.0 Soduim pyrosulfite g 5.0 Sodium pyrophosphate g 15.0 Sodium sulfate g 150.0 Potassium bromide g 2.0 Sodium hydroxide g 0.1 Formalin (37%) cc.. 15.0 Water added to make 1 liter.

First black & white developing solutions:

N-methyl-p-aminophenol g 5.0 Sodium sulfite g 70.0 Hydroquinone g 2.0 Sodium carbonate (monohydrate) g 41.0 Potassium bromide g 4.0 v Potassium thiocyanate g 1.6 Potassium iodide (0.1% aqueous solution) cc 10.0 Water added to make 1 liter. 1

Cyan color developing solution:

Potassium bromide g 3.0 6-nitrobenzimidazole g 0.03 Potassium iodide (0.1% aqueous solution) Sodium sulfite g 10.0 Sodium sulfate g 60.0 Potassium thiocyanate g 1.0 4-amino-3-methyl-N-ethyl-N-hydroxyethyl aniline sulfate g 2.5 Sodium hydroxide g 3.0 1,5-dihydroxy-2,6-dibromonaphthalene g 2.0 'Monobenzyl-p-aminophenol g 0.4 p-Aminophenol hydrochloride g 0.1 Water added to make 1 liter.

Yellow color development:

Sodium sulfite g 10.0 Potassium bromide g 0.5 Potassium iodide (0.1% aqueous solution) cc 25.0 fi-nitrobenzimidazole g 0.1 Sodium sulfate g 60.0 N,N-diethyl-p-phenylenediamine sulfite g 2.5 Sodium hydroxide ;g 2.5 w-Benzyl-4-(p-toluenesulfoamido)-acetanilidc Water added to make 1 liter.

Second black and white developing solution:

N-methyl-p-aminophenol sulfate g 1.0 Sodium sulfite g 50.0 Hydroquinone g 1.0 Sodium carbonate (monohydrate) g 41.0 Potassium bromide g 2.5 Water added to make 1 liter.

Magenta color developing solution:

'Sodium sulfite g 5.0 Potassium bromide g 1.0 Potassium thiocyanate -1 g 1.0 Sodium sulfate g 60.0 N,N-diethyl-3-methyl-p-phenylenediamine' hydrochloride g 2.5 Sodium hydroxide g 2.0 1-phenyl-3-(m-nitrobenzoylamino) 5 pyrazolone g 1.4 Ethylenediamine cc 8.0 Water added to make 1 liter.

Bleaching solution:

Ferricyanide g Potassium bromide g 30.0 Water added to make 1 liter.

Fixing solution:

Sodium thiosulfate g Sodium sulfite g 10 Water added to make 1 liter.

In the above-described reversal development, the following composition of this invention was added to the prehardening solution.

The photographic properties obtained as a result of the development are shown in the following table. The blue density (D and the red density (D of the unexposed part of the strips (maximum density part) are shown as the photographic properties. The blue density is the density of the uppermost blue-sensitive emulsion layer of the film which gives the yellow color by color development and the red density is the density of the lower-most red-sensitive emulsion layer which gives the cyan. If the values are large and not so dilferent from each other it means a good color balance and an image having good color reproduction.

Blue Red Test No density density As is clear from the table, by the addition of the compound of this invention, the blue density is increased without reducing the red density.

EXAMPLE 3 The photographic properties obtained as a result of the development are shown in the following table. The blue density and the red density photographic properties are shown below.

Blue Red density density As is clear from the table, by the addition of the compound of this invention the blue density is increased without reducing the red density.

EXAMPLE 4 A multiple layer type color photographic film consisting of three silver halide emulsion layers containing different couplers (cyan, yellow and magenta) and having different spectral sensitivities with each other was exposed by a sensitometer and then subjected to the following processings.

Tempera- Process ture, C.

. g Water washing The compositions of the processing solutions used above were as set forth below.

Color developing solution:

Sodium hexa-metaphosphate 'Benzyl alcohol Sodium sulfite Sodium carbonate Sodium hydroxide 4-amino 3 methyl-N-ethyl-N-methanesulf amidoethyl aniline sulfate g 5.0 Potassium bromide g 0.5 Water added to make 1 liter.

Stopping solution:

Acetic acid cc 25 Sodium acetate g 3 Potassium alum g 10 Water added to make 1 liter.

Bleaching solution:

Ferricyanide g 100 Potassium bromide g 20.0 Water added to make 1 liter.

Fixing solution:

Sodium thiosulfate g 150 Sodium sulfite g '10 Water added to make 1 liter.

In the negative color developing processings shown above, Compound 3 of this invention was added to the color developing solution in an amount of 5 x 10- mole/ liter.

On comparing the results thus obtained with those in which no compound of this invention was added, it was confirmed that by the addition of the compound of this invention, the uppermost blue-sensitive emulsion layer was not excessively developed and the development could 10 give good color balance among the red, green and blue densities.

EXAMPLE 5 In the developing processings in Example 1, a preliardening step and a neutralizing step were conducted before the first black & White development. The prehardening processing was conducted for 2 minutes and 30 seconds at 37 C. and the neutralizing process was carried out for 30 seconds at 37 C. The compositions of the processing solutions were as shown below. Pre-hardening solution:

Formalin (37% aqueous solution) cc 20 2,5-dimethoxytetrahydrofuran cc 4 Sulfuric acid cc 2 Sodium sulfate g Potassium bromide g 2 Borax g 5 Water added to make 1 liter.

Neutralizing solution:

Hydroxylamine sulfate g 20 Potassium bromide g 20 Glacial acetic acid cc 10 Sodium sulfate g 50 Sodium hydroxide g 6 Water added to make 1 liter.

In the above-described reversal color development, the compound of this invention was added to the neutralizing solution as shown in the following table.

The results obtained are shown in the following table, in which, as the photographic properties are shown the 'blue density and the red density at the maximum density and also the reversal sensitivity.

Maximum density Reversal sensitivity 1 Blue Red Blue Red density density density density 1 The reversal sensitivity was shown by the relative sensitivity when the sensitivity of the test No. 2 was assumed to be 100.

As shown in the above table, by the addition of the compound of this invention, the blue density was fully increased without giving any influence on the sensitivity and an image having better blue and red color balance was obtained.

EXAMPLE 6 To any acetyl cellulose film were applied a red-sensitive gelatino silver iodobromide emulsion containing a phenolic cyan coupler and further an intermediate gelatin layer. Then, a green-sensitive gelatino silver bromide emulsion containing a pyrazolone magenta coupler was applied to the intermediate layer and' further a yellow filter layer was formed on the layer. Then, a blue-sensitive gelatino silver iodobromide emulsion containing a keto-methylene yellow coupler was applied to the filter layer, and finally a protective gelatin layer was formed on the blue-sensitive emulsion layer.

Two kinds of the above-described color photographic films were prepared. One was a control sample and no compound of this invention was incorporated in any emulsion layers of the film but in the sample of this invention, 0.5 g./Ag mole of the Compound 3 of this invention was incorporated in the blue-sensitive emulsion layer of the photographic film.

Maximum density Reversal sensitivity 1 Blue Red Blue Red density density density density Control sample 2. 3 3. 3 145 106 Sample of invention. 3. 5 3. 5 100 100 1 The reversal sensitivity was shown by the relative sensitivity when the sensitivity obtained by the sample of this invention was assumed to be 100.

As shown in the above table, in the case of adding the compound of this invention, the blue density was sufliciently high even by the high temperature processings and an image having better color balance of the blue density and the red density was obtained.

What is claimed is:

1. In a high temperature rapid processing developing process for color photographic material which comprises subjecting an exposed multi-layer silver halide color photographic material to development at a temperature higher than 30 C., the improvement which comprises selectively inhibiting development of the uppermost photographic emulsion layer to improve the color balance and image quality of the developed photographic material by processing said color photographic material no later than development in the presence of an eifective development inhibitor for the uppermost photographic emulsion layer comprising a compound represented by general formula wherein R and R which may be the same or difi'erent, each is selected from the group consisting of a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, and a haloaryl group, and wherein R is selected from the group consisting of a hydrogen atom, a halogen atom, and an alkyl group.

2. In a high temperature rapid processing developing process for color photographic material comprising developing an exposed multi-layer silver halide color photographic material at a temperature higher than 30 C., the improvement which comprises selectively inhibiting the development of the uppermost photographic emulsion layer of said multi-layer silver halide color photographic material to improve the color balance and image quality of the developed photographic material by treating said photographic material no later than development with a solution containing an effective development inhibitor for the uppermost photographic emulsion layer comprising a compound represented by the formula Rs-C I 1 G-R 4. The process as claimed in claim 2, wherein said solution is a pro-hardening solution.

5. The process as claimed in claim 2, wherein said solution is a neutralizing solution.

6. The process as claimed in claim 2, wherein said temperature is higher than 35 C.

7. The process as claimed in claim 1, wherein said multi-layer silver halide color photographic material comprises a support having coated thereon, in succession, a red-sensitive photographic emulsion layer, a greensensitive photographic emulsion layer, a yellow filter layer and a blue-sensitive photographic emulsion layer.

8. The process as claimed in claim 2, wherein said multi-layer silver halide color photographic material comprises a support having coated thereon, in succession, a red-sensitive photographic emulsion layer, a green-sensitive photographic emulsion layer, a yellow filter layer and a blue-sensitive photographic emulsion layer.

9. The process as claimed in claim 3, wherein said developing solution is a black and white developing solution.

10. The process as claimed in claim 3, wherein said developing solution is a color developing solution.

11. The process as claimed in claim 1, wherein said compound is selected from the group consisting of 1,3,3a,7-tetraazaindene-4-thiol, 6-methyl-1,3,3a,7-tetraazaindene-4-thiol, 6-tertiary-butyl-1,3,3a,7-tetraazaindene-4-thiol, 6-pentyl-l,3,3a,7-tetraazaindene-4-thiol, 6-nonyl-1,3,3a,7-tetraazaindene-4-thiol,

6-undecyll,3,3a,7-tetraazaindene-4-thiol, 6-heptadecyl-1,3,3a,7-tetraazaindene-4-thiol, 6-phenyl-1,3,3a,7-tetraazaindene-4-thiol, 5-bromo-6-methyl-1,3,3a,7-tetraazaindene-4-thiol, 2,6-dimethyl-1,3,3a,7-tetraazaindene-4-thiol, 5-ethyl-6-methyl-1,3,3a,7-tetraazaindene-4-thiol and 5 -iso-butyl-6-methyl-1,3,3 a,7-tetraazaindene-4-thiol.

12. The process as claimed in claim 2, wherein said compound is selected from the group consisting of 1,3,3a,7-tetraazaindene-4-thiol,

6-methyll,3,3a,7-tetraazaindene-4-thiol, 6-tertiary-butyll ,3 3a,7-tetraazaindene-4-thiol, 6-pentyl-1,3,3a,7-tetraazaindene-4-thiol, 6-nonyl-1,3,3a,7-tetraazaindene-4-thiol, 6-undecyl-1,3,3a,7-tetraazaindene-4-thiol, 6-heptadecyl-1,3,3a,7-tetraazaindene-4-thiol, 6-phenyl-1,3,3a,7-tetraazaindene-4-thiol,

5 -bromo-6-methyl- 1,3,3 a,7-tetraazaindene-4-thiol, 2,6-dimethyl-1,3,3a,7-tetraazaindene-4-thiol, 5-eth'yl-6-methyl-l,3,3a,7-tetraazaindene-4-thiol, and 5-iso-butyl-6-methyl-1,3,3a,l-tetraazaindenel-thiol.

13. The process as claimed in claim 2, wherein said solution contains said compound in an amount of from 1 milligram to 1 gram of compound per liter of solution.

14. In a high temperature rapid processing developing process comprising developing an exposed multi-layer silver halide color photographic material at a temperature of greater than 30 C., the improvement consisting of selectively inhibiting development of the uppermost photographic emulsion layer to improve the color balance and image quality of the developed color photographic material by processing said color photographic material no later than development in a photographic solution containing from 1 milligram to 1 gram per liter of solution of an effective development inhibitor for the uppermost photographic emulsion layer consisting essentially of a compound selected from the group consisting of 1,3,3a,7-tetraazaindene-4-thiol,

6-methyll ,3,3a,7-tetraaZaindene-4-thiol, 6-tertiary-butyl-l,3,3a,7-teraazaindene-4-thiol, 6-pentyl-1,3,3a,7-tetraazaindene-4-thiol,

13 14 6-nony1-1,3,3a,7-tetraazaindene-4-thiol, 3,244,521 4/ 1966 Dersch et a1 9656.5 6-undecy1-L3,3a,7-tetraazaindene-4-thiol, 3,295,976 11/ 1967 Abbott et a1. 96-55 6-heptade'cyl-1,3,3a,7-tetraazaindene-4-thiol, 6-phenyl-1,3,3a,7-tetraazaindene-4thio1, FOREIGN F P S 5-bromo-6-methyl-1,3,3a,7-tetraazaindene-4-thiol, 5 893,428 4/ 1962* Great Bntam- 2,6-dimethyl-1,3,3a,7-tetraazaindene-4-thio1, OTHER REFERENCES 5-ethyl-6-methyl-1,3,3a,7-tetraazaindene-4-thio], and 5-iso-buty1-6-methy1-1,3,3a,7-tetraazaindene-4-thio1. g gg ggg$ i gi i g g chemlstry The References cted 10 NORMAN G. TORCHIN, Primary Examiner UNITED STATES PATENTS 2,956,876 10/1960 Spath 96-59 3,053,657 9/ 1962 GOOdchild et al 9656.5 US. Cl. X.R. 3,423,409 1/ 1969 Blatter 96-56.5 15 9655, 66

R. L. SOHILLING, Assistant Examiner 

